Nanoparticles In Aqueous Dispersion Research Articles

Acceptor-donor-acceptor-type molecules with large electrostatic potential difference for effective NIR photothermal therapy.

Although acceptor-donor-acceptor (A-D-A)-type molecules offer advantages in constructing NIR absorbing photothermal agents (PTAs) due to their strong intramolecular charge transfer and molecular planarity, their applications in photothermal therapy (PTT) of tumors remain insufficiently explored. In particular, the influence of ESP distribution on the optical properties of A-D-A photosensitizers has not been investigated. Herein, we analyze and compare the difference in ESP distribution between A-D-A-type small molecules and polymers to construct NIR absorbing PTAs with a high extinction coefficient (ε) and high photothermal conversion efficiency (PCE). The calculation results of density functional theory (DFT) indicate that the large ESP difference makes A-D-A-type small molecules superior to their polymer counterparts in realizing tight molecular packing and strong NIR absorbance. Among the as-prepared nanoparticles (NPs), Y6 NPs exhibited an obvious bathochromic shift of absorption peak from 711 nm to 822 nm, with the NIR-II emission extended to 1400 nm. Moreover, a high ε value of 5.69 L g-1 cm-1 and a PCE of 66.3% were attained, making Y6 NPs suitable for PTT. With a concentration of 100 μg mL-1, Y6 NPs in aqueous dispersion yielded a death rate of 93.4% for 4T1 cells upon 808 nm laser irradiation (1 W cm-2) for 10 min, which is comparable with the best results of recently reported PTT agents.

Electrolyte-induced aggregation of zein protein nanoparticles in aqueous dispersions

Ion specific effects on the charging and aggregation features of zein nanoparticles (ZNP) were studied in aqueous suspensions by electrophoretic and time-resolved dynamic light scattering techniques. The influence of mono- and multivalent counterions on the colloidal stability was investigated for positively and negatively charged particles at pH values below and above the isoelectric point, respectively. The sequence of the destabilization power of monovalent salts followed the prediction of the indirect Hofmeister series for positively charged particles, while the direct Hofmeister series for negatively charged ones assumed a hydrophobic character for their surface. The multivalent ions destabilized the oppositely charged ZNPs more effectively and the aggregation process followed the Schulze-Hardy rule. For some multivalent ions, strong adsorption led to charge reversal resulting in restabilization of the suspensions. The experimental critical coagulation concentrations (CCCs) could be well-predicted with the theory developed by Derjaguin, Landau, Verwey and Overbeek indicating that the aggregation processes were mainly driven by electrical double layer repulsion and van der Waals attraction. The ion specific dependence of the CCCs is owing to the modification of the surface charge through ion adsorption at different extents. These results are crucial for drug delivery applications, where inorganic electrolytes are present in ZNP samples.

Interaction of Serum Albumin and Fatty Acid Molecules with Graphenes of Shungite Carbon Nanoparticles in Aqueous Dispersion Assessed by Raman Spectroscopic Analysis of Water in the High Wavenumber Region

Interaction of Serum Albumin and Fatty Acid Molecules with Graphenes of Shungite Carbon Nanoparticles in Aqueous Dispersion Assessed by Raman Spectroscopic Analysis of Water in the High Wavenumber Region

Stabilizing both oil droplets and titanium dioxide nanoparticles in aqueous dispersion with nanofibrillated cellulose

Nanocellulose is a well-known stabilizer for several colloidal dispersions, including emulsions and solid nanoparticles, replacing surfactants, polymers, and other additives, and therefore providing more minimalistic and eco-friendly formulations. However, could this ability be extended to stabilize oil droplets and inorganic nanoparticles simultaneously in the same colloidal system? This work aimed to answer this question. We evaluated both cationic and anionic nanofibrillated celluloses to stabilize both titanium dioxide nanoparticles and oil droplets. The resulting suspensions held their macroscopic stability for up to 2 months, regardless of pH or surface charge. Cryo-TEM images revealed a complex network formation involving nanofibers and TiO2 nanoparticles, which agrees with the high viscosity values and gel-like behavior found in rheology measurements. We propose that the formation of this network is responsible for the simultaneous stabilization of oil droplets and TiO2 nanoparticles, and that this may be used as a formulation tool for other complex systems.

Pluronic stabilized conjugated polymer nanoparticles for NIR fluorescence imaging and dual phototherapy applications

• Pluronic stabilized conjugated polymer nanoparticles (CP-NP-Plu) are prepared. • CP-NP-Plu present photothermal conversion efficiency of 61% under NIR irradiation. • 2-fold increase of singlet oxygen generation quantum yield due to encapsulation with Plu • NIR fluorescence imaging ability validated at single nanoparticle level. Besides their intensive application as solar photovoltaic materials, low bandgap conjugated polymers have been recently exploited in cell imaging and phototherapeutic applications due to their photoactivity in the near-infrared (NIR) spectral domain, also known as the “biologically transparent window”. Herein, Poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta [2,1-b;3,4-b′]dithiophene)-alt-4,7(2,1,3-benzothiadiazole) (PCPDTBT) conjugated polymer was used to prepare novel NIR activatable theranostic nanoparticles, via nanoprecipitation method, for fluorescence imaging and dual photothermal-photodynamic therapy (PTT-PDT) applications. To overcome the drawback of hydrophobicity of PCPDTBT, the approach of encapsulating the obtained nanoparticles with a layer of Pluronic F127 amphiphilic block co-polymer was herein applied. The Pluronic layer not only provides excellent colloidal stability, but also ensures enhanced fluorescence emission, improved photothermal heating and singlet oxygen generation ability of the nanoparticles in aqueous dispersion. Specifically, upon irradiation with a NIR laser at 785 nm, the obtained nanoparticles exhibit good thermal response and excellent photostability leading to a photothermal conversion efficiency of 61%. Moreover, a near two-fold increase in the singlet oxygen generation quantum yield due to encapsulation with Pluronic is also detected. Furthermore, fluorescence imaging measurements on single nanoparticle immobilized on glass substrate reveal their potential as fluorescence contrast agents. The enhanced fluorescence and improved therapeutic properties of our nanoparticles suggest the possibility to be employed as NIR activatable theranostic agents via dual phototherapy combined with high-resolution fluorescence tracking.

Water-Dispersible Fe3O4 Nanoparticles Modified with Controlled Numbers of Carboxyl Moieties for Magnetic Induction Heating

Monodisperse Fe3O4 nanoparticles (NPs) with excellent water dispersibility and stability were prepared by the introduction of the carboxyl group (−COOH) on the surface of the as-prepared oleyl-capped Fe3O4 NPs. Controlled introduction of the COOH moieties on the NP surface was carried out by a simple ligand exchange reaction using two types of phosphonic acid ligands with dodecyl moiety and the terminal COOH group. The degree of modification of the COOH group on the particle surface was controlled by tuning the molar ratios of the two phosphonic acids. During the ligand exchange reaction, no change was observed in the crystal structure and morphology of the Fe3O4 NPs. The results of Fourier transform infrared (FT-IR) spectroscopy confirmed that the two ligands were bound to the Fe3O4 NP surface through their phosphoric acid functional groups. The surface coverage and molar ratios of the two ligands were evaluated by thermal gravimetric analysis (TGA) and via proton nuclear magnetic resonance (1H NMR) measurements, respectively. Results obtained from the thermal analyses were consistent with the initial molar ratios of the ligands used in the reaction, which reflect on the efficiency of the developed ligand exchange process. Our COOH-modified Fe3O4 NPs could be dispersed in water by deprotonation for over 6 months and exhibit a typical ferrofluid behavior without the addition of other surfactants and dispersants, showing high dispersion stability. Furthermore, the magnetic induction heating performance of the Fe3O4 NPs in aqueous dispersions was evaluated and the specific absorption rate (SAR) value was estimated to be 38.3 W/g Fe. These results suggest that our COOH-modified Fe3O4 NPs with the desired number of COOH surface moieties can be advantageous for applications such as precise surface design, water-based ferrofluid, and hyperthermia treatment.

Combination of carotenoids from Spirulina and PLA/PLGA or PHB: New options to obtain bioactive nanoparticles

The use of poly-β-hydroxybutyrate (PHB) is an alternative polymer that can be considered environment friendly and renewable to prepare nanoparticles of carotenoids. This study aimed to develop and characterize aqueous dispersion nanoparticles and lyophilized nanoparticles of carotenoid extract obtained from Spirulina sp. LEB 18 by nanoprecipitation, using poly d,l-lactic acid (PLA)/poly d,l-lactic-co-glycolic acid (PLGA) (75:25 w/w) or PHB as encapsulants. The samples were characterized for the particle size, polydispersity index, zeta potential, apparent viscosity, pH, color parameters, ultraviolet–visible (UV/Vis) spectrophotometry, carotenoid profile, encapsulation efficiency, morphology, and thermal analysis. Nanoparticles containing microalgae carotenoid extract showed average particle diameter on a nanoscale (<200 nm), high homogeneity and stability, high thermal stability, and encapsulation efficiency carotenoid (>80%) when compared to nanoparticles containing β-carotene synthetic. PHB or PLA/PLGA as encapsulating material in the production of nanoparticles from microalgae carotenoids can be a polymeric alternative capable of promoting greater stability and application of carotenoids.

PEDOT:PSS nano-particles in aqueous media: A comparative experimental and molecular dynamics study of particle size, morphology and z-potential

PEDOT:PSS is the most widely used conducting polymer in organic and printed electronics. PEDOT:PSS films have been extensively studied to understand the morphology, ionic and electronic conductivity of the polymer. However, the polymer dispersion, which is used to cast or spin coat the films, is not well characterized and not well understood theoretically. Here, we study in detail the particle morphology, size, charge density and zeta potential (z-potential) by coarse-grained MD simulations and dynamic light scattering (DLS) measurements, for different pH levels and ionic strengths. The PEDOT:PSS particles were found to be 12 nm–19 nm in diameter and had a z-potential of −30 mV to −50 mV when pH was changed from 1.7 to 9, at an added NaCl concentration of 1 mM, as measured by DLS. These values changed significantly with changing pH and ionic strength of the solution. The charge density of PEDOT:PSS particles was also found to be dependent on pH and ionic strength. Besides, the distribution of different ions (PSS−, PEDOT+, Na+, Cl−) present in the solution is simulated to understand the particle morphology and molecular origin of z-potential in PEDOT:PSS dispersion. The trend in change of particle size, charge density and z- potential with changing pH and ionic strength are in good agreement between the simulations and experiments. Our results show that the molecular model developed in this work represents very well the PEDOT:PSS nano-particles in aqueous dispersion. With this study, we hope to provide new insight and an in-depth understanding of the morphology and z-potential evolution in PEDOT:PSS dispersion.

Fatty acid transfer between serum albumins and shungite carbon nanoparticles and its effect on protein aggregation and association.

The bioactivity of the natural ultrafine carbon form shungite nanocarbon (ShC) is of particular interest both for biomedical applications of such nanomaterials and their negative impact on the aquatic environmental. Here we studied the interaction of serum albumin (SA) with ShC nanoparticles in aqueous dispersion with respect to its structural-dynamic, thermodynamic, and hydrodynamic effects. Electron spin resonance (EPR) with a 5-DOXYL-stearic acid spin probe (5DSA) demonstrates that ShC can affect fatty acid (FA) binding by SA, protein conformation in the stearic FA spin probe binding region, and protein aggregation due to the partial transfer of FA to the ShC nanoparticles. The ratio of SA fractions changes in the presence of ShC in favor of the fraction that is less saturated with FA as shown by differential scanning calorimetry (DSC). The stability of interaction with ShC is significantly higher for aggregates of SA molecules that carry physiological amounts of FA, compared to aggregates of the FA-free protein, as studied by dynamic light scattering (DLS) analysis. Generally, the mixed dispersion of SA and ShC nanoparticles is more homogeneous than the SA solution alone. This is manifested both in the size of the molecular associates and in the microenvironment of the protein-bound FA. The formation of the SA-ShC interface is likely to result in a greater uniformity of the FA binding sites and a decrease in protein fractions and "hot patches" on the protein surface responsible for the supramolecular heterogeneity of the protein in solution.

Quantifying the photothermal conversion efficiency of plasmonic nanoparticles by means of terahertz radiation

The accurate determination of the photothermal response of nanomaterials represents an essential aspect in many fields, such as nanomedicine. Specifically, photothermal cancer therapies rely on the precise knowledge of the light-to-heat transfer properties of plasmonic nanoparticles to achieve the desired temperature-induced effects in biological tissues. In this work, we present a novel method for the quantification of the photothermal effect exhibited by nanoparticles in aqueous dispersions. By combining the spatial and temporal thermal dynamics acquired at terahertz frequencies, the photothermal conversion efficiency associated with the geometry of the plasmonic nanoparticles can be retrieved in a noncontact and noninvasive manner. The proposed technique can be extended to the characterization of all those nanomaterials which feature a temperature-dependent variation of the refractive index in the terahertz regime.

Periodic Polyethylene Sulfonates from Polyesterification: Bulk and Nanoparticle Morphologies and Ionic Conductivities

A series of polyethylene-like ionomers with periodic sulfonate groups were synthesized by polyesterification of octatetracontane-1,48-diol and tetrabutylammonium dimethyl sulfosuccinate. Optional cation exchange in aqueous dispersions replaced the NBu4+ counterions for Na+ or Cs+. The defined periodic microstructure of the polymers leads to the formation of layered structures in bulk and to platelet-like self-stabilized nanoparticles in aqueous dispersion, as observed by X-ray scattering and transmission electron microscopy. The bulk polymers exhibit a semicrystalline structure with multiple stacks of ionic layers embedded in the crystallites with a layer-to-layer distance of 50–60 A. Upon melting, the ionic layers in the NBu4+-neutralized polymer transitioned to disordered ionic aggregates, while the layered ionic aggregates in the Cs+- and Na+-neutralized polymers transformed into ionic aggregates with hexagonal symmetry, which is an unprecedented order-to-order transition in microphase-separated ionome...

SURFACE MODIFICATION OF TITANIUM DIOXIDE NANOPARTICLES WITH ACRYLIC ACID/ISOBUTYLENE COPOLYMER UNDER ULTRASONIC TREATMENT

The influence of the ultrasonic treatment of block copolymer solution on its solid-liquid interface behavior was investigated in detail. The surface modification of titanium dioxide nanoparticles in aqueous dispersions of specially tailor-made periodic acrylic acid/isobutylene copolymer by ultrasonic treatment was studied in order to get new approaches for the creation of hybrid composite materials or polymer coatings. The pigment surface modification by the above copolymer was comparatively investigated regarding conventional adsorption as contrasted to an ultrasonic treatment assisted procedure. The course and efficiency of the polymer adsorption onto the pigment surface were quantified by electrokinetic sonic amplitude measurements. The higher efficiency of the pigment surface coating by the copolymer as achieved by ultrasonic treatment in comparison to conventional adsorption is a consequence of ultrasonically induced pigment surface activation. Two perspective avenues of the utilization of the discovered effects for creation of organic-inorganic composite materials are anticipated: the nanoparticles could first be treated by ultrasound in the presence of polymers and so create a surface modifying coating and the second option is an entrainment of the nanoparticles into the monomer matrix which can be polymerized afterward yielding a polymer with immobilized nanoparticles.

Thermodiffusion of citrate-coated γ-Fe2O3 nanoparticles in aqueous dispersions with tuned counter-ions - anisotropy of the Soret coefficient under a magnetic field.

Under a temperature gradient, the direction of thermodiffusion of charged γ-Fe2O3 nanoparticles (NPs) depends on the nature of the counter-ions present in the dispersion, resulting in either a positive or negative Soret coefficient. Various counter-ions are probed in finely tuned and well characterized dispersions of citrate-coated NPs at comparable concentrations of free ionic species. The Soret coefficient ST is measured in stationary conditions together with the mass-diffusion coefficient Dm using a forced Rayleigh scattering method. The strong interparticle repulsion, determined by SAXS, is also attested by the increase of Dm with NP volume fraction Φ. The Φ-dependence of ST is analyzed in terms of thermophoretic and thermoelectric contributions of the various ionic species. The obtained single-particle thermophoretic contribution of the NPs (the Eastman entropy of transfer ŝNP) varies linearly with the entropy of transfer of the counter-ions. This is understood in terms of electrostatic contribution and of hydration of the ionic shell surrounding the NPs. Two aqueous dispersions, respectively, with ST > 0 and with ST < 0 are then probed under an applied field H[combining right harpoon above], and an anisotropy of Dm and of ST is induced while the in-field system remains monophasic. Whatever the H[combining right harpoon above]-direction (parallel or perpendicular to the gradients and ), the Soret coefficient is modulated keeping the same sign as in zero applied field. In-field experimental determinations are well described using a mean field model of the interparticle magnetic interaction.

Thermoresponsive Behavior of Magnetic Nanoparticle Complexed pNIPAm-co-AAc Microgels

Characterization of responsive hydrogels and their enhancement with novel moieties have improved our understanding of functional materials. Hydrogels coupled with inorganic nanoparticles have been sought for novel types of responsive materials, but the efficient routes for the formation and the responsivity of complexed materials remain for further investigation. Here, we report that responsive poly(N-isopropylacrylamide-co-acrylic acid) (pNIPAm-co-AAc) hydrogel microparticles (microgels) are tunable by varying composition of co-monomer and crosslinker as well as by their complexation with magnetic nanoparticles in aqueous dispersions. Our results show that the hydrodynamic diameter and thermoresponsivity of microgels are closely related with the composition of anionic co-monomer, AAc and crosslinker, N,N′-Methylenebisacrylamide (BIS). As a composition of hydrogels, the higher AAc increases the swelling size of the microgels and the volume phase transition temperature (VPTT), but the higher BIS decreases the size with no apparent effect on the VPTT. When the anionic microgels are complexed with amine-modified magnetic nanoparticles (aMNP) via electrostatic interaction, the microgels decrease in diameter at 25 °C and shift the volume phase transition temperature (VPTT) to a higher temperature. Hysteresis on the thermoresponsive behavior of microgels is also measured to validate the utility of aMNP-microgel complexation. These results suggest a simple, yet valuable route for development of advanced responsive microgels, which hints at the formation of soft nanomaterials enhanced by inorganic nanoparticles.

Photocatalytic Degradation and Hydrogen Production of TiO2/Carbon Fiber Composite Using Bast as a Carbon Fiber Source

TiO2/carbon fiber composite is achieved by loading TiO2 nanoparticles on biomass carbon fiber, which originates from the carbonized natural bast. The carbonized process and the loading amount of TiO2 are researched in detail. It is found that the carbonized bast fiber shows robust adsorption characteristics for TiO2 nanoparticles in aqueous dispersion, and TiO2 nanoparticles with ~15 wt.% in total weight are uniformly loaded onto the fiber surface. The photocatalytic properties of TiO2/carbon fiber composite are evaluated by photocatalytic degradation of rhodamine B and water splitting for hydrogen production. The results indicate that 90% RhB molecules could be attacked in 60 min under UV light irradiation, and the hydrogen production rate of water splitting is up to 338.51 μmol/h. The highlight is that TiO2/carbon fiber composite is easy to be recycled due to the incorporation of macroscopical biomass carbon fiber.

Curvature dependence of the effect of ionic functionalization on the attraction among nanoparticles in dispersion.

Solubilization of nanoparticles facilitates nanomaterial processing and enables new applications. An effective method to improve dispersibility in water is provided by ionic functionalization. We explore how the necessary extent of functionalization depends on the particle geometry. Using molecular dynamics/umbrella sampling simulations, we determine the effect of the solute curvature on solvent-averaged interactions among ionizing graphitic nanoparticles in aqueous dispersion. We tune the hydrophilicity of molecular-brush coated fullerenes, carbon nanotubes, and graphane platelets by gradually replacing a fraction of the methyl end groups of the alkyl coating by the ionizing -COOK or -NH3Cl groups. To assess the change in nanoparticles' dispersibility in water, we determine the potential-of-mean-force profiles at varied degrees of ionization. When the coating comprises only propyl groups, the attraction between the hydrophobic particles intensifies from spherical to cylindrical to planar geometry. This is explained by the increasing fraction of surface groups that can be brought into contact and the reduced access to water molecules, both following the above sequence. When ionic groups are added, however, the dispersibility increases in the opposite order, with the biggest effect in the planar geometry and the smallest in the spherical geometry. These results highlight the important role of geometry in nanoparticle solubilization by ionic functionalities, with about twice higher threshold surface charge necessary to stabilize a dispersion of spherical than planar particles. At 25%-50% ionization, the potential of mean force reaches a plateau because of the counterion condensation and saturated brush hydration. Moreover, the increase in the fraction of ionic groups can weaken the repulsion through counterion correlations between adjacent nanoparticles. High degrees of ionization and concomitant ionic screening gradually reduce the differences among surface interactions in distinct geometries until an essentially curvature-independent dispersion environment is created. Insights into tuning nanoparticle interactions can guide the synthesis of a broad class of nonpolar nanoparticles, where solubility is achieved by ionic functionalization.

Fluorescence Detection of Zinc Oxide Nanoparticles in Water Contamination Analysis based on Surface Reactivity with Porphyrin

A simple rapid analytical method for determining the concentration of ZnO nanoparticles in aqueous dispersion has been developed by adding porphyrin (TCPP) as a fluorophore into the water sample for fluorescence analysis. Quenching of the emission intensity at 650 nm provides a Stern-Volmer plot with adequate sensitivity for the detection of ZnO nanoparticles from 0.15 mg/mL up to 1.5 mg/mL. A new emission peak at 605 nm can be attributed to the formation of a unique ZnO-TCPP complex. This unique emission peak is good for both identification and quantitation of ZnO nanoparticles at low concentrations down to 0.0015 mg/mL. The new method affords a linear dynamic range up to 1.2 mg/mL.

Water dispersions of natural graphene based carbon nanoparticles: ESR spin probe study

Dynamic and phase behavior of an aqueous dispersion of shungite carbon (ShC) nanoparticles, one of natural graphene-like nanomaterials structured in a special way in an aqueous medium, is of considerable interest, as in the case of other carbon nanomaterials, due to its effects and presumable technological and biomedical applications. ShC nanoparticles in aqueous dispersions of different composition were studied in the temperature range 7–60°C using electron spin resonance (ESR) technique of stable spin probes. Hydrophobic probe 5-DOXYL stearic acid was introduced into the structure of hydrated ShC nanoparticles. Hydrophilic probe 4-oxo-TEMPO was dissolved in the surrounding bulk solvent. It is assumed that an increase in the immobilization of the hydrophobic probe in the presence of NaCl, urea, HCl, NaOH, sucrose is associated with a change in the state of hydration of ShC nanoparticles. At the same time, an increase in the carbon concentration during the evaporation of water did not cause changes in the dynamics of the probe until the nanoparticles were dehydrated. Changes in hydration of the hydrophobic probe on the ShC nanoparticles at a temperature of about 17–20°C can be associated with a change in the state of nanoparticle dispersion near the critical mixing temperature of the main and metastable phases. The sigmoid type Arrhenius dependence of the mobility of both the hydrophilic and hydrophobic probes has maximum steepness in the region of the supercritical mesophase near 37°C. The structural and dynamic variations of the dispersion associated with the change in the dynamic regime in the supercritical mesophase near the Frenkel line are discussed as a probable explanation. The data obtained are interpreted on the basis of a hypothetical phase diagram of the dispersion of fullerenes and ShC nanostructures.

Synthesis of poly(glycerol adipate)-g-oleate and its ternary phase diagram with glycerol monooleate and water

Poly(glycerol adipate) (PGA) was synthesized by enzymatic polymerization and grafted with different amounts of oleoyl chloride. A series of graft copolymers PGA-g-Ox was obtained where O represents the oleate side chains and x is the degree of grafting (mol% of the pendant OH groups of PGA esterified) ranging from 11 to 90. Small angle X-ray scattering (SAXS) data revealed nanophase separation of the oleate side chains into nanodomains in bulk and wide angle X-ray scattering (WAXS) profiles showed a broad halo, reflecting the amorphous nature of the synthesized graft polymers. Glycerol monooleate (GMO), an amphiphilic lipid with one hydrophobic oleate tail and a glycerol hydrophilic head group, self-assembles into various liquid crystalline phases in the presence of water. Since oleate chains are integral part of both GMO and the graft copolymers, a certain degree of miscibility can be expected influencing the self-assembly behavior. Using SAXS for phase identification, systematic studies were carried out at room temperature on the ternary system of GMO/PGA-g-O22/water and the ternary phase diagram was constructed. The addition of polymer did influence the phase behavior of the GMO/water system. The water in the lamellar and cubic mesophases was partially replaced by PGA-g-O22. Furthermore, keeping the GMO/water ratio constant at 1:1, the addition of PGA-g-O22 lead to swelling of the water channels in the inverse bicontinuous Pn3m cubic phase. Preliminary investigations on the potential application of PGA-g-O22 as a stabilizer of structured nanoparticles in aqueous dispersions were carried out employing different transmission electron microscopy techniques.

Bovine Serum Albumin Adsorption on TiO2 Colloids: The Effect of Particle Agglomeration and Surface Composition.

Protein adsorption at nanostructured oxides strongly depends on the synthesis conditions and sample history of the material investigated. We measured the adsorption of bovine serum albumin (BSA) to commercial Aeroxide TiO2 P25 nanoparticles in aqueous dispersions. Significant changes in the adsorption capacity were induced by mild sample washing procedures and attributed to the structural modification of adsorbed water and surface hydroxyls. Motivated by the lack of information about the sample history of commercial TiO2 nanoparticle samples, we used vapor-phase-grown TiO2 nanoparticles, a well-established model system for adsorption and photocatalysis studies, and performed on this material for the first time a systematic and quantitative BSA adsorption study. After alternating vacuum and oxygen treatment of the nanoparticle powders at elevated temperatures for surface purification, we determined size distributions covering both the size of the individualized nanoparticles and nanoparticle agglomerates using transmission electron microscopy (TEM), X-ray diffraction (XRD), and dynamic light scattering (DLS) in an aqueous dispersion. Quantitative BSA adsorption measurements at different pH values and thus variable combinations of surface-charged proteins and TiO2 nanoparticles revealed a consistent picture: BSA adsorbs only at the outer agglomerate surfaces without penetrating the interior of the agglomerates. This process levels at coverages of single monolayers, which resist consecutive simple washing procedures. A detailed analysis of the protein-specific IR amide bands reveals that the adsorption-induced protein conformational change is associated with a decrease in the helical content. This study underlines that robust qualitative and quantitative statements about protein adsorption and corona formation require well-documented and controllable surface properties of the nanomaterials involved.